全文获取类型
收费全文 | 7105篇 |
免费 | 164篇 |
国内免费 | 15篇 |
专业分类
化学 | 3991篇 |
晶体学 | 167篇 |
力学 | 300篇 |
数学 | 861篇 |
物理学 | 1965篇 |
出版年
2023年 | 46篇 |
2022年 | 108篇 |
2021年 | 120篇 |
2020年 | 120篇 |
2019年 | 166篇 |
2018年 | 116篇 |
2017年 | 137篇 |
2016年 | 194篇 |
2015年 | 148篇 |
2014年 | 192篇 |
2013年 | 510篇 |
2012年 | 366篇 |
2011年 | 420篇 |
2010年 | 251篇 |
2009年 | 220篇 |
2008年 | 304篇 |
2007年 | 322篇 |
2006年 | 261篇 |
2005年 | 261篇 |
2004年 | 241篇 |
2003年 | 147篇 |
2002年 | 129篇 |
2001年 | 90篇 |
2000年 | 67篇 |
1999年 | 78篇 |
1998年 | 61篇 |
1996年 | 66篇 |
1995年 | 66篇 |
1994年 | 65篇 |
1993年 | 85篇 |
1992年 | 78篇 |
1991年 | 56篇 |
1990年 | 70篇 |
1989年 | 69篇 |
1988年 | 71篇 |
1987年 | 65篇 |
1986年 | 43篇 |
1985年 | 85篇 |
1984年 | 110篇 |
1983年 | 73篇 |
1982年 | 81篇 |
1981年 | 83篇 |
1980年 | 103篇 |
1979年 | 89篇 |
1978年 | 89篇 |
1977年 | 94篇 |
1976年 | 77篇 |
1975年 | 58篇 |
1974年 | 59篇 |
1973年 | 67篇 |
排序方式: 共有7284条查询结果,搜索用时 15 毫秒
101.
Gupta D Roitzsch M Lippert B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6643-6652
Isocytosine (ICH; 1) exists in solution in an equilibrium of tautomers 1a and 1b with the N1 and N3 positions carrying the acidic proton, respectively. In the solid state, both tautomers coexist in a 1:1 ratio. As we show, the N3H tautomer 1b can selectively be crystallized in the presence of the model nucleobase 1-methylcytosine (1-MeC). The complex 1b x (1-MeC)2 x H2O (2) forms pairs through three hydrogen bonds between the components; hydrogen bonds between identical molecules are also formed, leading to an infinite tape structure. On the other hand, the N1H tautomer 1a co-crystallizes with protonated ICH to give [1a x ICH2]NO3 (3), again with three hydrogen bonds between the partners, yet the acidic proton is disordered over the two entities. With M(II)(dien) (M=Pt, Pd; dien=diethylenetriamine) preferential coordination of tautomer 1a through the N3 position is observed. DFT calculations, which were also extended to Pt(II)(tmeda) linkage isomers (tmeda=N,N,N',N'-tetramethylethylenediamine), suggest that intramolecular hydrogen bonding between the ICH tautomers and the co-ligands at M, while adding to the preference for N3 coordination, is not the major determining factor. Rather it is the inherently stronger Pt-N3 bond which favors complexation of 1a. With an excess of M(II)(dien), dinuclear species [M2(dien)2(IC-N1,N3)]3+ (M=Pd(II), 4 and Pt(II), 5) also form and were isolated as their ClO4(-) salts and structurally characterized. In strongly acidic medium 5 is converted to [Pt(dien)(ICH-N1)]2+ (6), that is, to the Pt(II) complex of tautomer 1b. 相似文献
102.
The various thermodynamic parameters for the periodate oxidation of six anilines, viz. aniline, p-chloroaniline, p-ethoxyaniline, o- and p-methoxyanilines and p-methylaniline have been reported and discussed. The validity of the isokinetic relationship and various linear free energy relationships (LFERs) have been tested and discussed. An attempt has been made to correlate these findings with the mechanism operative in these reactions. 相似文献
103.
The diffusion length of charge carriers in the active layer of a perovskite solar cell (PSC) of the structure Glass/PEDOT: PSS/CH3NH3PbI3/PC60BM/Al is modelled. It is found that the diffusion length depends on the position x in the active layer measured from the PEDOT: PSS interface, Urbach energy and temperature. By varying the voltage in the range from zero to , it is shown that the dependence of diffusion length on the position x in the active layer reduces at higher voltage. The combined influence of applied voltage and temperature on the diffusion length of charge carriers is investigated and it is found that in the low voltage range the diffusion length is temperature independent, but it becomes significantly temperature dependent at higher voltages. Also, it is found that the diffusion length decreases as the applied voltage increases and this reduction becomes much more significant at higher voltage and temperatures. The combined influence of applied voltage and Urbach energy on diffusion length of charge carriers reveals that the diffusion length decreases when both the applied voltage and Urbach energy increase. However, the reduction in the diffusion length due to the increase in Urbach energy becomes less significant at higher voltage. 相似文献
104.
Chandra S Gupta LK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1089-1094
Nickel(II) complexes, having the general composition Ni(L)2X2, have been synthesized [where L: isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-]. All the Ni(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and mass spectral studies. All the complexes were found to have magnetic moments corresponding to two unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic and infrared spectral studies. Newly synthesized ligand and its nickel(II) complexes have been screened against different bacterial and fungal growth. 相似文献
105.
Rajuru R. Reddy Agarala S. R. Reddy Vanka Krishna Reddy 《Theoretical chemistry accounts》1985,67(3):187-191
The bond dissociation energies for Alkali halides have been estimated based on the derived relations: $$\begin{gathered} D_{AB} = \bar D_{AB} + 31.973{\text{ e}}^{0.363\Delta x} {\text{ and}} \hfill \\ D_{AB} = \bar D_{AB} (1 - 0.2075\Delta xr_e ) + 52.29\Delta x, \hfill \\ \end{gathered} $$ where \(\bar D_{AB} = (D_{AA} \cdot D_{BB} )^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} \) , Δx represents Pauling electronegativity differences x(A ?xB) and r e is the internuclear distance. A simplified formula relating bond orders, q, to spectroscopic constants is suggested. The formula has the form q = 1.5783 × 10?3 (ω e 2 re/ Be)1/2. The ambiguity arising from the Parr and Borkman relation is discussed. The present study supports the view of Politzer that q/(0.5r e)2 is the correct definition of bond order. The estimated bond energies and bond orders are in reasonably good agreement with the literature values. The bond energies estimated with the relations we suggested, for alkali halides give an error of 4.5% and 5.3%, respectively. The corresponding error associated with Pauling's equation is 40.2%. 相似文献
106.
Ramaswamy K Saito H Murakami H Shiba K Suga H 《Journal of the American Chemical Society》2004,126(37):11454-11455
Fx3 is an artificial ribozyme with the ability to aminoacylate various tRNAs with phenylalanine and its nonnatural derivatives. Herein we report a simple strategy to build tRNA specificity into the generic Fx3, by appending to its 3'-end a tRNA-specific sequence (TSS), which is complementary to the acceptor stem of the cognate tRNA. This new designer ribozyme, referred to as Fx10, is able to recognize its cognate tRNA via a 10-base-pair interaction that is formed after the invasion of the tRNA acceptor stem by the TSS. We have demonstrated that Fx10 can aminoacylate its cognate tRNA with a high degree of specificity and also discriminate against the noncognate tRNAs. Because the tRNA specificity can be easily programmed into Fx10, it is a custom-made catalyst to generate nonnatural aminoacyl-tRNAs. 相似文献
107.
Krishna C. Joshi Renuka Jain Anshu Dandia Vandana Sharma 《Journal of heterocyclic chemistry》1986,23(1):97-99
A novel system 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione has been synthesized by the treatment of fluorinated isatins with thiocarbohydrazide in aqueous ethanolic medium. Under exactly similar conditions, N-acetylisatin gave exclusively thiocarbohydrazone. The spiro product, on treatment with acetic acid, gave fluorinated isoindigo. Characterization of these products have been done by elemental analyses, ir, pmr and mass spectral studies. 相似文献
108.
Abstract— Recently, a new technique of 1O2 generation has been described by Midden and Wang. The sensitizer is immobilized on silica gel particles which are attached on one surface of a glass plate which is placed, sensitizer-side down, above a solution leaving a small air space between the sensitizer and the solution. Applying the principle of the technique, i.e. generation of 1O2 in the gas phase above the solution, we first improved the long-term stability of the dye (rose bengal) by using double stock transparent tape instead of rubber cement. Under these conditions, although the initial rate of production was higher in rubber cement, the rate of production reached a plateau after 30 min, whereas with double stick transparent tape, the rate of generation was linear up to 100 min. This result was explained by the fact that silica glass beads are embedded in the cement which could lead to the bleaching reaction of the dye. Different reactions have been investigated, the bleaching of N,N-dimethyl-4-nitrosoaniline (RNO) in the presence of imidazole, destruction of anthracenedipropionic acid, formation of a stable nitroxide from a sterically hindered secondary amine and the influence of pH on the nitroxide yield. The yield was measured to be 5 × 1012 molecules of singlet oxygen produced per second per cm2 from the surface of the plate using the RNO bleaching reaction. This method of generating 1O2 also seems promising for studying the killing of mammalian cells by 1O2 as the sole damaging species. 相似文献
109.
R. S. Saxena Reshma D. Parikh K. C. Gupta 《Monatshefte für Chemie / Chemical Monthly》1984,115(2):141-146
Potentiometric and conductometric studies on the zinc, cadmium, lead—methylene bis thio acetic acid system in aqueous media reveal the formation of 1:1 and 1:2 (M:L) complexes in thepH range 3.4–5.1. Their stability constants have been determined at 20°, 30° and 40 °C by applyingCalvin andMelchior's extension ofBjerrum's method. The overall changes in thermodynamic function H, G and S accompanying complexation have been evaluated at 30 °C.
Elektrochemische Untersuchungen über Zusammensetzung, Stabilität und Thermodynamik von Zn(II)-, Cd(II)- und Pb(II)-Komplexen mit Methylen-bisthioessigsäure
Zusammenfassung Potentiometrische und konduktometrische Untersuchungen an Zink-, Cadmium- und Blei-Methylen-bis-thioessigsäure-Systemen in wäßrigem Medium zeigten die Bildung von 1:1 und 1:2 (M:L)-Komplexen impH-Bereich 3,4–5,1. Die Stabilitätskonstanten wurden bei 20°, 30° und 40 °C mittels derCalvin-Melchior-Methode (erweiterteBjerrum-Methode) bestimmt. Die thermodynamischen Parameter H, G und S der Komplexierung wurden für 30 °C ermittelt.相似文献
110.
A new, simple, precise, and rapid high-performance thin-layer chromatographic method was developed for the determination of 6 benzodioxanes in Piper mullesua extract: 1',3'-benzodioxole-5'-(2,4,8-triene-isobutyl nonanoate), 1',3'-benzodioxole-5'-(2,4,12-triene-isobutyl tridecanoate), fargesin, sesamin, asarinin, 1',3'-benzodioxole-5'-(2,4,8-triene-methyl nonanoate). The ingredients were separated on a precoated Silica Gel 60 F254 plate with a solvent system of toluene-acetone (92 + 8). The 6 benzodioxanes were well separated and easily identified in this chromatographic system. The separated benzodioxanes were visualized by color development with a spray reagent consisting of 1 g vanillin dissolved in 100 mL H2SO4-ethanol (5 + 95, v/v). Quantitation was performed by scanning the spots and comparing the integrated areas of compounds in samples with those of standards. Recoveries from samples spiked with known amounts of the benzodioxanes were excellent. The results were comparable with those estimated by liquid chromatography. 相似文献